CN112619694A - Process for preparing olefin catalyst - Google Patents
Process for preparing olefin catalyst Download PDFInfo
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- CN112619694A CN112619694A CN201910955427.XA CN201910955427A CN112619694A CN 112619694 A CN112619694 A CN 112619694A CN 201910955427 A CN201910955427 A CN 201910955427A CN 112619694 A CN112619694 A CN 112619694A
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- molecular sieve
- ssz
- ion exchange
- methanol
- temperature
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 38
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000002808 molecular sieve Substances 0.000 claims abstract description 109
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 109
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 94
- 238000002425 crystallisation Methods 0.000 claims abstract description 61
- 230000008025 crystallization Effects 0.000 claims abstract description 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 47
- 239000013078 crystal Substances 0.000 claims abstract description 37
- 238000003756 stirring Methods 0.000 claims abstract description 36
- 238000002360 preparation method Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001868 water Inorganic materials 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000005342 ion exchange Methods 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 239000011734 sodium Substances 0.000 claims description 38
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 37
- 229910052708 sodium Inorganic materials 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000000499 gel Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000000741 silica gel Substances 0.000 claims description 15
- 229910002027 silica gel Inorganic materials 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 239000005977 Ethylene Substances 0.000 claims description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 239000012159 carrier gas Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical group [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 4
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 239000011362 coarse particle Substances 0.000 claims 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- -1 ammonia ions Chemical class 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 238000010791 quenching Methods 0.000 description 8
- 230000000171 quenching effect Effects 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 description 5
- 229960003805 amantadine Drugs 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005216 hydrothermal crystallization Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003245 coal Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/635—0.5-1.0 ml/g
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y40/00—Manufacture or treatment of nanostructures
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention provides a small-grain catalyst for preparing olefin from methanol and a preparation method thereof. The method comprises the following steps: uniformly mixing sodium hydroxide, water, a template agent and an auxiliary agent at normal temperature, and adding an aluminum source; after an aluminum source is dissolved, sequentially adding a silicon source and seed crystals, and violently stirring to obtain gel; and crystallizing the gel, cooling after crystallization, separating crystallized products, drying a solid sample, roasting, exchanging ammonia ions, and roasting again to obtain the hydrogen type SSZ-13 molecular sieve, namely the methanol-to-olefin catalyst. Compared with the conventional preparation method of the micron-sized SSZ-13 molecular sieve, the SSZ-13 molecular sieve obtained by the invention has the advantages of small grain size, high crystallinity, regular appearance, large specific surface area, good diffusion performance, excellent catalytic performance for preparing olefin from methanol and excellent carbon deposition resistance.
Description
Technical Field
The invention relates to a preparation method of a silicon-aluminum molecular sieve, in particular to a preparation method of a small-grain methanol-to-olefin molecular sieve, belonging to the technical field of catalyst preparation.
Background
Low-carbon olefins such as ethylene and propylene are important basic chemical raw materials, are widely used for synthesizing plastics and petrochemical products, and occupy a very important position in national economy. The traditional main production routes of ethylene and propylene are petroleum routes of naphtha and light hydrocarbon cracking and FCC catalytic cracking. Because the energy structure characteristics of China are rich in coal, less in oil and poor in gas, the development of a technology (MTO) for preparing methanol and then producing low-carbon olefins by taking coal as a basic raw material becomes an important direction for producing ethylene and propylene. Meanwhile, the development of the MTO technology is beneficial to the cleanness and high-added-value utilization of coal, realizes the diversification of the production raw materials of coal instead of oil and low-carbon olefin, and has profound significance for guaranteeing the national energy safety.
The heart of the MTO technology is the catalyst. Among them, SAPO-34 molecular sieve has higher methanol conversion rate and ethylene, propylene selectivity, and is approved as a special catalyst for preparing olefin from methanol. In recent years, SSZ-13 molecular sieve has been researched and found to have the CHA type topological structure same as that of SAPO-34 molecular sieve, and to show MTO catalytic performance similar to that of SAPO-34 molecular sieve under relatively low reaction temperature condition, and to be paid much attention without considering the problems of phosphorus pollution of waste catalyst and the like.
With the continuous and deep research of MTO process, the slowing of the deactivation of the catalyst is an important way for improving the performance of the MTO catalyst, and the improving of the molecular diffusion performance of the molecular sieve is the most effective means for slowing the coking and deactivation of the MTO catalyst. In particular, the small-grain molecular sieve has more advantages in the aspects of diffusion mass transfer and the like, and becomes an important direction for the synthesis research of the MTO catalyst.
The patent CN201010178372.5 provides a preparation method of a small-crystal-grain SAPO-34 molecular sieve, the method comprises the steps of carrying out hydrothermal synthesis on gel, carrying out aging treatment, carrying out hydrogen peroxide oxidation treatment, and finally carrying out ultrasonic dispersion and vacuum drying to obtain the small-crystal-grain SAPO-34 molecular sieve, wherein the crystal grain size of the product is 300-500 nm. The experimental conditions of the invention are easy to control, but the aging process is more complex, two sections of aging processes are needed, and the mother liquor is separated and water is supplemented before the second section of aging, so that the operation process is not beneficial to industrial scale-up production.
Patent CN201310237106.9 proposes a method for promoting synthesis of small-grained molecular sieve by adding defect-structure seed crystal. The method comprises the step of carrying out hydrothermal crystallization on an initial crystallization liquid at the temperature of 200-250 ℃ for 1-10 hours to obtain the SAPO-34 crystal seeds with more lattice defects. After solid-liquid separation, performing hydrothermal treatment at 140-170 ℃ for 0.1-4 h to dissolve the crystal seeds into fine fragments with structure orientation and crystal nucleus effects, and then heating to 180-250 ℃ to continue hydrothermal crystallization to obtain a small-crystal-grain SAPO-34 molecular sieve product. However, the method requires higher crystallization temperature and higher material requirement on the reaction kettle.
The patent CN201210150289.6 realizes the synthesis of the small-grain SAPO-34 molecular sieve by a multi-stage temperature control crystallization method. The method comprises the following steps: (1) stirring and aging the crystallized liquid at the temperature of T1 of 20-100 ℃ for 1-24 hours; (2) carrying out hydrothermal crystallization on the aged crystallization liquid at the temperature of T2 of 180-250 ℃ for 1-20 hours; (3) the temperature is reduced to T3 to be between room temperature and 160 ℃ by program, and the temperature is kept for at least 0.1 hour; (4) and (3) heating the mixture to the temperature T4 of 180-250 ℃, and carrying out hydrothermal crystallization for 2-24 hours to obtain a small-grain molecular sieve product.
Patent CN201711293430.7 reports a method for synthesizing small-grain SAPO-34 molecular sieve by multi-step crystallization. The method comprises the steps of preparing SAPO-34 synthetic gel by a conventional method, crystallizing for 0.5-5 hours at 170-250 ℃, cooling to 50-150 ℃, crystallizing for 0.5-5 hours, and finally heating to 180-250 ℃ for crystallizing for 5-240 hours to obtain the small-grain SAPO-34 molecular sieve. Both methods need strict temperature control program operation on the reaction kettle, and the large-scale industrial reaction kettle has slow temperature rise and reduction process, so that the industrial application is difficult to realize.
Patent CN201310511412.7 proposes a method for preparing small-grain SAPO-34 molecular sieve by multistage crystallization. The method comprises the steps of dividing crystallization temperature into three sections from low to high, enabling the crystallization temperature of the two adjacent sections to be different, enabling the crystallization temperature of the later section to be at least 40 ℃ higher than that of the former section, further providing a scheme that crystallization is carried out for 5-10 hours at 25-35 ℃, crystallization is carried out for 10-20 hours at 100-150 ℃, crystallization is carried out for 10-45 hours at 150-200 ℃, and the total crystallization time is controlled to be 30-90 hours, so that the SAPO-34 molecular sieve with the uniform size of 400-800 nm can be obtained. The method has better feasibility of controlling the industrial amplification crystallization temperature, but the temperature rise process of a large industrial reaction kettle is slow, and the total crystallization time is still difficult to control.
Patent CN200910067691.6 prepares SAPO-34 molecular sieve with small particle size, large specific surface area and high crystallinity by adding structure directing agents of triethylamine and fluoride (such as sodium fluoride, ammonium fluoride or hydrogen fluoride), but the fluoride is toxic and the wastewater is difficult to treat.
The patent CN201310093558.4 prepares the low-silicon nano SAPO-34 molecular sieve by a microwave hydrothermal crystallization method, but the microwave crystallization method has not realized the industrial application.
Currently, few reports are made on the synthesis of SSZ-13 molecular sieves suitable for methanol-to-olefin synthesis. From the existing research results, the microwave method and the ultrasonic method have not realized industrial application, the multi-stage crystallization of the molecular sieve is difficult to realize the industrial production control, the addition of fluoride is easy to cause pollution, and the addition of other organic dispersing agents and guiding agents increases the synthesis cost of the molecular sieve. In addition, the SSZ-13 molecular sieve is different from the SAPO-34 molecular sieve, so that the synthesis method of the small-crystal SAPO-34 molecular sieve is difficult to be suitable for guiding the synthesis of the small-crystal SSZ-13 molecular sieve. Therefore, the development of a simple and effective method for synthesizing the small-grain SSZ-13 molecular sieve which is suitable for industrial amplification is an urgent problem to be solved.
Disclosure of Invention
The invention aims to solve the technical problems that in the process of synthesizing the SSZ-13 molecular sieve in the prior art, the crystal grain size of the SSZ-13 molecular sieve product is larger and the MTO reaction activity is lower, so that the invention provides a preparation method of the small-crystal SSZ-13 molecular sieve suitable for the MTO reaction. The method has the advantages of simplicity, feasibility, suitability for industrial scale-up production, small crystal grain size of the obtained SSZ-13 molecular sieve and high MTO reaction activity.
The invention provides a preparation method of an olefin catalyst, which comprises the following steps:
step (1): mixing a template agent, an auxiliary agent, sodium hydroxide and water, and stirring and mixing uniformly to obtain a mixed solution; adding an aluminum source into the mixed solution, and stirring until the aluminum source is dissolved; adding a silicon source into the mixed solution, and keeping vigorous stirring to obtain gel; wherein the content of the first and second substances,calculated by oxide, the molar ratio of the silicon source, the aluminum source, the sodium hydroxide, the template agent, the auxiliary agent and the water is 100SiO2∶(0.5～2)Al2O3∶(10～20)Na2O, (4-15) template agent, (0.1-2) auxiliary agent, (800-2400) H2O；
Step (2): placing the gel obtained in the step (1) in a hydrothermal reaction kettle, carrying out dynamic crystallization treatment, and carrying out centrifugal separation, washing, drying and roasting on the obtained product to obtain a sodium Na-SSZ-13 molecular sieve;
and (3): and (3) performing ammonia ion exchange, drying and roasting on the sodium type Na-SSZ-13 molecular sieve obtained in the step (2) to obtain a hydrogen type H-SSZ-13 molecular sieve, namely the small-grain methanol-to-olefin catalyst.
In the preparation method of the olefin catalyst provided by the invention, preferably, the template agent is N, N, N-trimethyl adamantammonium, and the auxiliary agent is tetraethylammonium chloride, tetraethylammonium bromide or tetraethylammonium iodide.
In the preparation method of the olefin catalyst provided by the invention, preferably, the aluminum source is aluminum hydroxide, aluminum sulfate, aluminum isopropoxide, pseudo-boehmite or sodium metaaluminate or a mixture of any two of the aluminum hydroxide, the aluminum sulfate, the aluminum isopropoxide, the pseudo-boehmite or the sodium metaaluminate, and preferably aluminum hydroxide.
In the preparation method of the olefin catalyst provided by the invention, preferably, the silicon source is nano silica, silica sol, white carbon black or coarse silica gel or a mixture of any two of the nano silica, the silica sol, the white carbon black and the coarse silica gel, and the coarse silica gel is preferred.
The preparation method of the olefin catalyst provided by the invention comprises the following step (1), preferably, adding a seed crystal after adding a silicon source, wherein the seed crystal is calcined sodium Na-SSZ-13 or hydrogen H-SSZ-13, the addition amount of the seed crystal is 0-5% of the mass of the silicon source, and the value of the seed crystal is not 0.
The preparation method of the olefin catalyst provided by the invention is characterized in that the conditions of dynamic crystallization treatment are preferably that the rotating speed of a motor is 20-60 rpm/min, the crystallization temperature is 150-180 ℃, and the crystallization time is 4-8 days.
In the preparation method of the olefin catalyst provided by the present invention, it is preferable that the calcination conditions in the step (2) are: the roasting temperature is 550-600 ℃, the roasting time is 4-10 hours, and the heating rate is 0.5-2 ℃/min; preferably at a temperature of 600 c, preferably for a time of 4 hours, preferably at a temperature rise rate of 1 c/min.
In the preparation method of the olefin catalyst provided by the present invention, preferably, the conditions of the ammonia ion exchange in the step (3) are: 1 to 2mol/L NH40.01 to 0.2g of Na-SSZ-13/ml NH in an aqueous Cl solution4The Cl aqueous solution is subjected to ion exchange at the temperature of 60-80 ℃, the time of single ion exchange is 0.5-3 h, and the ion exchange times are 2-4; preferably 1mol/L NH4Aqueous Cl solution, 0.05g Na-SSZ-13/ml NH4Cl aqueous solution, ion exchange temperature of 70 ℃, single ion exchange time of 2h and ion exchange times of 3.
In the preparation method of the olefin catalyst provided by the present invention, it is preferable that the calcination conditions in step (3) are: the roasting temperature is 500-550 ℃, the roasting time is 4-6 hours, and the heating rate is 0.5-2 ℃/min.
The invention also provides an olefin catalyst which is prepared by the preparation method of the olefin catalyst.
The olefin catalyst provided by the invention is composed of silicon and aluminum, the particle size is less than 1 mu m, in some embodiments, the particle size is less than 200nm, and the crystal morphology of the catalyst is cubic or cubic stacked body.
The invention also provides a method for preparing olefin from methanol, which comprises the following steps: tabletting and sieving the small-crystal-grain methanol-to-olefin catalyst, taking out the sieved catalyst, loading the catalyst into a fixed bed reactor, introducing nitrogen carrier gas with the flow rate of 30-100 mL/min, activating at 450-550 ℃ for 0.5-2 h, cooling to methanol-to-olefin reaction conditions, keeping the flow rate of the nitrogen carrier gas, and introducing methanol to obtain ethylene and propylene.
The reason why the catalyst is tableted and sieved is that catalyst particles are very small, and below 200nm, the catalyst can be agglomerated to form unstable small particles under normal conditions, and the unstable small particles can be dispersed into smaller particles and flow when being blown by nitrogen gas flow or other gas flow in a reactor, so that the catalyst is blown away from the reactor by the gas flow, the catalyst loss is caused, and meanwhile, the MTO reaction evaluation result is inaccurate. The small catalyst is tabletted to form a stable catalyst sheet, the catalyst sheet is extruded by a sieve with a larger mesh to obtain a large-particle molecular sieve with uniform and stable size, the influence of airflow on the large-particle molecular sieve in a reactor is small, the large-particle molecular sieve is not easily blown away by the airflow, the catalyst is not easily lost, the catalyst MTO reaction is stable, and the evaluation result is accurate.
The method for preparing the olefin from the methanol, provided by the invention, preferably comprises the reaction conditions of 330-420 ℃ of reaction temperature, 0.1-0.8 MPa of reaction pressure (absolute pressure) and 0.5-5.0 h of mass space velocity of the methanol-1And the mass concentration of the methanol is 50-95%.
The present invention can be described in detail as follows:
a preparation method of a small-grain catalyst for preparing olefin from methanol comprises the following steps:
(1) mixing the template agent, the auxiliary agent, the sodium hydroxide and the water, and stirring and mixing uniformly;
(2) adding an aluminum source into the mixed solution, and stirring until the aluminum source is dissolved;
(3) adding a silicon source and seed crystals into the mixed solution in sequence, and keeping vigorous stirring to obtain gel;
(4) placing the gel completely stirred in a hydrothermal reaction kettle, carrying out dynamic crystallization treatment, and carrying out centrifugal separation, washing, drying and roasting on the obtained product to obtain a sodium Na-SSZ-13 molecular sieve;
(5) and the Na-SSZ-13 molecular sieve is subjected to ammonia ion exchange, drying and roasting to obtain the hydrogen type H-SSZ-13 molecular sieve.
In the preparation method of the small-grain catalyst for preparing olefin from methanol, the reaction material aluminum source is Al2O3The silicon source is SiO2Calculated as Na, sodium hydroxide2Calculated by O, the template agent is N, N, N-trimethyl amantadine ammonium calculated by TMADAOH, the auxiliary agent is calculated by R, and each reaction material is 100SiO according to the molar ratio2∶0.5～2Al2O3∶10～20Na2O∶4～15TMAdaOH∶0.1～2R∶800～2400H2O。
In the preparation method, the aluminum source is aluminum hydroxide, aluminum sulfate, aluminum isopropoxide, pseudo-boehmite, sodium metaaluminate or a mixture of any two of the aluminum hydroxide, the aluminum sulfate, the aluminum isopropoxide, the pseudo-boehmite and the sodium metaaluminate, and the aluminum hydroxide is preferred.
In the preparation method of the invention, the silicon source is nano silicon dioxide, silica sol, white carbon black and coarse pore silica gel or a mixture of any two of the nano silicon dioxide, the silica sol, the white carbon black and the coarse pore silica gel, and the coarse pore silica gel is preferred.
In the preparation method, the auxiliary agent is tetraethylammonium chloride, tetraethylammonium bromide or tetraethylammonium iodide.
In the preparation method, the seed crystal is calcined Na-SSZ-13 or hydrogen H-SSZ-13, and the addition amount of the seed crystal is 0-5% of the mass of the silicon source.
In the preparation method, the conditions of the dynamic crystallization treatment are that the rotating speed of a motor is 20-60 rpm/min, the crystallization temperature is 150-180 ℃, and the crystallization time is 4-8 days.
In the preparation method, the roasting conditions (step 4) of the sodium Na-SSZ-13 molecular sieve are that the roasting temperature is 550-600 ℃, the roasting time is 4-10 hours, the heating rate is 0.5-2 ℃/min, the preferred temperature is 600 ℃, the time is 4 hours, and the heating rate is 1 ℃/min.
In the preparation method, the condition of ammonia ion exchange is 1-2 mol/L NH40.01 to 0.2g of Na-SSZ-13/ml (NH) as an aqueous Cl solution4Cl aqueous solution), the ion exchange temperature is 60-80 ℃, the time of single ion exchange is 0.5-3 h, the ion exchange frequency is 2-4, and 1mol/L NH is preferred4Aqueous Cl solution, 0.05g Na-SSZ-13/ml (NH)4Aqueous solution of Cl), the ion exchange temperature is 70 ℃, the single ion exchange time is 2h, and the ion exchange times are 3 times.
In the preparation method, the roasting conditions (step 5) of the hydrogen type H-SSZ-13 molecular sieve are that the roasting temperature is 500-550 ℃, the roasting time is 4-6 hours, the heating rate is 0.5-2 ℃/min, the temperature is preferably 550 ℃, the time is 4 hours, and the heating rate is 1 ℃/min.
In the preparation method, the small-grain methanol-to-olefin catalyst is a calcined hydrogen type H-SSZ-13 molecular sieve.
According to the inventionThe small-grain methanol-to-olefin catalyst can be directly used in an MTO reaction process, and the MTO reaction evaluation process is realized by the following steps: tabletting the hydrogen type H-SSZ-13 molecular sieve after powdery roasting, sieving by a sieve of 60-80 meshes, taking out 1g of the sieved molecular sieve sample, putting the sieved molecular sieve sample into a fixed bed reactor, introducing nitrogen carrier gas with the flow of 30-100 ml/min, activating at 450-550 ℃ for 0.5-2H, cooling to the reaction condition of preparing olefin from methanol, keeping the flow of the nitrogen carrier gas, and introducing methanol to obtain ethylene and propylene with higher concentration. The reaction conditions are as follows: the reaction temperature is 330-420 ℃, the reaction pressure (absolute pressure) is 0.1-0.8 MPa, and the mass space velocity of methanol is 0.5-5.0 h-1And the mass concentration of the methanol is 50-95%.
The catalyst for preparing olefin from small-grain methanol and the preparation method thereof are characterized in that the catalyst for preparing olefin from small-grain methanol is composed of silicon and aluminum, the grain size is less than 1 mu m and even less than 100nm, the crystal morphology is a cube or a cubic stack body, the catalyst can be directly used as an MTO reaction catalyst, and the catalyst has the characteristics of good MTO activity stability and high selectivity of ethylene and propylene.
Drawings
FIG. 1 is an X-ray diffraction (XRD) spectrum of a sample of molecular sieve;
FIG. 2 is a Scanning Electron Microscope (SEM) picture of a molecular sieve sample;
FIG. 3 shows the results of MTO reaction evaluation of the samples.
Detailed Description
The following examples further illustrate the present invention, but the scope of the present invention is not limited thereto.
Comparative example 1
This comparative example provides a process for the preparation of a conventional SSZ-13 zeolite, which comprises the following synthetic steps:
weighing 44g of trimethyl amantadine ammonium (25 wt%) and 3g of sodium hydroxide, adding 79.5g of deionized water, and stirring and mixing uniformly; adding 1.4g of aluminum hydroxide into the solution, and stirring vigorously for 10 minutes; and after the aluminum source is completely dissolved, slowly adding 32g of coarse silica gel, and continuously and violently stirring for 2h to form gel. Transferring the obtained gel to stainless steel crystallization kettle with polytetrafluoroethylene lining at 160 deg.CDynamic crystallization is carried out for 6 days, and the rotating speed of a motor is 30 rpm/min. And after crystallization is finished, taking out the crystallization kettle, quenching the crystallization kettle by water to room temperature, centrifugally separating the product, washing the product to be neutral, drying the product in a dryer at 100 ℃ for 5 hours, and roasting the product at 550 ℃ for 10 hours at the heating rate of 1 ℃/min to obtain the sodium type molecular sieve. Then placing the roasted sodium type molecular sieve sample in NH with the concentration of 1mol/L4Ion exchange is carried out for 3 times in Cl solution, the exchange temperature is 70 ℃, the time of single ion exchange is 2h, and the ion exchange capacity is 0.05g (sodium type molecular sieve)/ml (NH)4Cl solution). And (3) drying the product after ion exchange at 100 ℃ for 5 hours after centrifugal separation, and roasting at 550 ℃ for 4 hours at the heating rate of 1 ℃/min to obtain the hydrogen type molecular sieve, which is recorded as SZ-1.
XRD results show that the obtained SZ-1 product is an SSZ-13 molecular sieve, has high crystallinity and does not have mixed crystals; SEM results show that the SZ-1 product has larger grain size and the average grain diameter is about 8 mu m.
Example 1
Weighing 50.9g of trimethyl amantadine ammonium (25 wt%), 0.57g of tetraethylammonium chloride and 7.2g of sodium hydroxide, adding 89.5g of deionized water, and stirring and mixing uniformly; 1.56g of aluminum hydroxide is added into the solution and stirred vigorously for 10 minutes; and after the aluminum source is completely dissolved, slowly adding 38.4g of coarse silica gel, and continuously and violently stirring for 2 hours to form gel. Transferring the obtained gel to a stainless steel crystallization kettle with a polytetrafluoroethylene lining, and dynamically crystallizing for 7 days at 160 ℃ at the motor rotating speed of 30 rpm/min. After crystallization, the crystallization kettle is taken out and cooled to room temperature by water quenching, the product is centrifugally separated and washed to be neutral, dried for 5 hours at 100 ℃ in a dryer, and then roasted for 10 hours at 550 ℃ at the heating rate of 1 ℃/min to obtain the sodium type molecular sieve, which is marked as Na-SZ-2 and can be used as the seed crystal of the following examples.
Placing the roasted sodium type molecular sieve sample in NH with the concentration of 1mol/L4Ion exchange is carried out for 3 times in Cl solution, the exchange temperature is 70 ℃, the time of single ion exchange is 2h, and the ion exchange capacity is 0.05g (sodium type molecular sieve)/ml (NH)4Cl solution). The product after ion exchange is centrifugally separated, dried for 5 hours at 100 ℃, roasted for 4 hours at 550 ℃ at the heating rate of 1 ℃/min to obtain the hydrogen type molecular sieve, and recordedIs SZ-2.
XRD results show that the obtained SZ-2 product is an SSZ-13 molecular sieve, has high crystallinity and does not have mixed crystals; SEM results show that the SZ-2 product has smaller grain size, the grain size distribution is in the range of 80nm-1 μm, and partial agglomeration exists.
Example 2
Weighing 50.9g of trimethyl amantadine ammonium (25 wt%), 0.57g of tetraethylammonium chloride and 7.2g of sodium hydroxide, adding 89.5g of deionized water, and stirring and mixing uniformly; 1.56g of aluminum hydroxide is added into the solution and stirred vigorously for 10 minutes; after the aluminum source is completely dissolved, 38.4g of coarse silica gel is slowly added, after 10 minutes of vigorous stirring, 0.72g of seed crystal (SZ-1) is added, and then vigorous stirring is continued for 2 hours to form gel. Transferring the obtained gel to a stainless steel crystallization kettle with a polytetrafluoroethylene lining, and dynamically crystallizing for 6 days at 160 ℃ at the motor rotating speed of 30 rpm/min. After crystallization, the crystallization kettle is taken out and cooled to room temperature by water quenching, the product is centrifugally separated and washed to be neutral, dried for 5 hours at 100 ℃ in a dryer, and then roasted for 10 hours at 550 ℃ at the heating rate of 1 ℃/min to obtain the sodium type molecular sieve, which is marked as Na-SZ-3 and can be used as the seed crystal of the following examples.
Placing the roasted sodium type molecular sieve sample in NH with the concentration of 1mol/L4Ion exchange is carried out for 3 times in Cl solution, the exchange temperature is 70 ℃, the time of single ion exchange is 2h, and the ion exchange capacity is 0.05g (sodium type molecular sieve)/ml (NH)4Cl solution). And (3) drying the product after ion exchange at 100 ℃ for 5 hours after centrifugal separation, and roasting at 550 ℃ for 4 hours at the heating rate of 1 ℃/min to obtain the hydrogen type molecular sieve, wherein the molecular sieve is recorded as SZ-3.
XRD results show that the obtained SZ-3 product is an SSZ-13 molecular sieve, has high crystallinity and does not have mixed crystals; SEM results show that the SZ-3 product has uniform particle size, average size of about 90nm, no agglomeration and cubic morphology.
Example 3
59.4g of trimethyl adamantammonium (25 wt%), 1.0g of tetraethylammonium iodide and 8.4g of sodium hydroxide are weighed, 104.4g of deionized water is added, and the mixture is stirred and mixed uniformly; adding 1.1g of aluminum hydroxide into the solution, and stirring vigorously for 10 minutes; after the aluminum source is completely dissolved, 44.8g of coarse silica gel is slowly added, after 10 minutes of vigorous stirring, 0.84g of seed crystal (Na-SZ-2) is added, and then vigorous stirring is continued for 2 hours to form gel. Transferring the obtained gel to a stainless steel crystallization kettle with a polytetrafluoroethylene lining, and dynamically crystallizing for 6 days at 160 ℃ at the motor rotating speed of 30 rpm/min. And after crystallization is finished, taking out the crystallization kettle, quenching the crystallization kettle by water to room temperature, centrifugally separating the product, washing the product to be neutral, drying the product in a dryer at 100 ℃ for 5 hours, and roasting the product at 550 ℃ for 10 hours at the heating rate of 1 ℃/min to obtain the sodium type molecular sieve.
Placing the roasted sodium type molecular sieve sample in NH with the concentration of 1mol/L4Ion exchange is carried out for 3 times in Cl solution, the exchange temperature is 70 ℃, the time of single ion exchange is 2h, and the ion exchange capacity is 0.05g (sodium type molecular sieve)/ml (NH)4Cl solution). And (3) drying the product after ion exchange at 100 ℃ for 5 hours after centrifugal separation, and roasting at 550 ℃ for 4 hours at the heating rate of 1 ℃/min to obtain the hydrogen type molecular sieve, which is recorded as SZ-4.
XRD results show that the obtained SZ-4 product is an SSZ-13 molecular sieve, has high crystallinity and does not have mixed crystals; SEM results show that the average size of the SZ-4 product is about 60 nm.
Example 4
Weighing 127.2g of trimethyl adamantammonium (25 wt%), 1.1g of tetraethylammonium chloride and 18g of sodium hydroxide, adding 223.7g of deionized water, and stirring and mixing uniformly; adding 1.3g of aluminum hydroxide into the solution, and stirring vigorously for 10 minutes; after the aluminum source is completely dissolved, 96g of coarse silica gel is slowly added, after vigorous stirring for 10 minutes, 1.92g of seed crystal (SZ-2) is added, and then vigorous stirring is continued for 2 hours to form gel. Transferring the obtained gel to a stainless steel crystallization kettle with a polytetrafluoroethylene lining, and dynamically crystallizing for 6 days at 160 ℃ at the motor rotating speed of 30 rpm/min. And after crystallization is finished, taking out the crystallization kettle, quenching the crystallization kettle by water to room temperature, centrifugally separating the product, washing the product to be neutral, drying the product in a dryer at 100 ℃ for 5 hours, and roasting the product at 550 ℃ for 10 hours at the heating rate of 1 ℃/min to obtain the sodium type molecular sieve.
Placing the roasted sodium type molecular sieve sample in NH with the concentration of 1mol/L4Ion exchange in Cl solution for 3 times, and cross-linkingThe exchange temperature is 70 ℃, the single ion exchange time is 2h, and the ion exchange capacity is 0.05g (sodium type molecular sieve)/ml (NH)4Cl solution). And (3) drying the product after ion exchange at 100 ℃ for 5 hours after centrifugal separation, and roasting at 550 ℃ for 4 hours at the heating rate of 1 ℃/min to obtain the hydrogen type molecular sieve, which is recorded as SZ-5.
XRD results show that the obtained SZ-5 product is an SSZ-13 molecular sieve, has high crystallinity and does not have mixed crystals; SEM results show that the average size of the SZ-5 product is about 80nm, and the agglomeration is less.
Example 5
And (3) evaluating the catalytic activity of the molecular sieve MTO reaction.
The MTO reaction performance of the molecular sieve catalysts obtained in comparative example 1 and examples 1, 2, 3 and 4 was examined by using a fixed bed micro-reaction apparatus. The evaluation method comprises the following steps: and tabletting and crushing the hydrogen type molecular sieve sample by using a mould, sieving by using a 60-80-mesh sieve, collecting 1g of sieved molecular sieve sample, and filling the upper end and the lower end of the molecular sieve with quartz sand treated by concentrated nitric acid. Before reaction, the catalyst needs to be pretreated, nitrogen carrier gas with the flow rate of 50ml/min is introduced, the temperature of a reactor is increased to 500 ℃ from normal temperature for 1h and is kept for 1h, then the temperature is reduced to 350 ℃, and reaction material methanol is introduced, the mass concentration of the reaction material methanol is 60%, and the mass space velocity is 1.5h-1The reaction pressure was 0.1MPa (absolute).
TABLE 1 measurement of specific surface area of molecular sieve sample
As can be seen from the results of table 1 and fig. 2, the specific surface area of the small-grained molecular sieve sample is not much different from that of the large-grained comparative sample, but mesopores are formed due to the stacking effect of the small grains, so that the molecular sieve has a certain mesopore volume.
TABLE 2 sample MTO product distribution
Reaction times were all 120 min.
The evaluation results of the samples are shown in FIG. 3.
As can be seen from the results of table 2 and fig. 3, when the small-crystallite SSZ-13 molecular sieve provided by the present invention is used in the MTO reaction, the selectivity of ethylene and propylene is significantly improved and the MTO reaction life is prolonged as compared to the molecular sieve catalyst sample of the comparative example.
Example 6
Weighing 23.4g of trimethyl amantadine ammonium (25 wt%), 2.5g of tetraethylammonium chloride and 11.5g of sodium hydroxide, adding 184.7g of deionized water, and stirring and mixing uniformly; adding 1.6g of aluminum hydroxide into the solution, and stirring vigorously for 10 minutes; after the aluminum source was completely dissolved, 138.6g of silica sol was slowly added, after vigorous stirring for 10 minutes, 2.13g of seed crystal (Na-SZ-3) was added, and then vigorous stirring was continued for 2 hours to form a gel. Transferring the obtained gel to a stainless steel crystallization kettle with a polytetrafluoroethylene lining, and dynamically crystallizing for 8 days at 150 ℃ at the motor rotating speed of 20 rpm/min. And after crystallization is finished, taking out the crystallization kettle, quenching the crystallization kettle by water to room temperature, centrifugally separating the product, washing the product to be neutral, drying the product in a dryer at 100 ℃ for 5 hours, and roasting the product at 600 ℃ for 4 hours at the heating rate of 1 ℃/min to obtain the sodium type molecular sieve.
Placing the calcined sodium type molecular sieve sample in NH with the concentration of 2mol/L4Ion exchange is carried out for 2 times in Cl solution, the exchange temperature is 80 ℃, the time of single ion exchange is 3h, and the ion exchange capacity is 0.01g (sodium type molecular sieve)/ml (NH)4Cl solution). And (3) drying the product after ion exchange at 100 ℃ for 5 hours after centrifugal separation, and roasting at 500 ℃ for 6 hours at the temperature rise rate of 2 ℃/min to obtain the hydrogen type molecular sieve. The obtained product is an SSZ-13 molecular sieve, the grain size of the product is about 200nm, and the specific surface area is 662m2(ii) in terms of/g. The molecular sieve is activated for 2 hours under the conditions of nitrogen carrier gas flow rate of 100ml/min and temperature of 450 ℃ and then subjected to MTO reaction evaluation, wherein the mass concentration of methanol is 50 percent, and the space velocity of the methanol is 5 hours-1Reaction pressure 0.8MPa, reaction temperature 3Under the condition of 30 ℃, the mass selectivity of ethylene and propylene in the pyrolysis gas respectively reaches 35.06 percent and 45.08 percent.
Example 7
Weighing 110.1g of trimethyl adamantammonium (25 wt%), 0.2g of tetraethylammonium bromide and 7.3g of sodium hydroxide, adding 42.6g of deionized water, and stirring and mixing uniformly; 2.8g of aluminum hydroxide is added into the solution and stirred vigorously for 10 minutes; after the aluminum source is completely dissolved, 53.4g of coarse silica gel is slowly added, after 10 minutes of vigorous stirring, 1.6g of seed crystal (SZ-3) is added, and then vigorous stirring is continued for 2 hours to form gel. Transferring the obtained gel to a stainless steel crystallization kettle with a polytetrafluoroethylene lining, and dynamically crystallizing for 4 days at 180 ℃ at the motor rotating speed of 60 rpm/min. And after crystallization is finished, taking out the crystallization kettle, quenching the crystallization kettle by water to room temperature, centrifugally separating the product, washing the product to be neutral, drying the product in a dryer at 100 ℃ for 5 hours, and roasting the product at 600 ℃ for 4 hours at the heating rate of 1 ℃/min to obtain the sodium type molecular sieve.
Placing the roasted sodium type molecular sieve sample in NH with the concentration of 1.5mol/L4Ion exchange is carried out for 2 times in Cl solution, the exchange temperature is 80 ℃, the time of single ion exchange is 0.5h, and the ion exchange capacity is 0.2g (sodium type molecular sieve)/ml (NH)4Cl solution). And (3) drying the product after ion exchange at 100 ℃ for 5 hours after centrifugal separation, and roasting at 500 ℃ for 6 hours at the heating rate of 0.5 ℃/min to obtain the hydrogen type molecular sieve. The obtained product is an SSZ-13 molecular sieve, the grain size of the product is about 300nm, and the specific surface area is 667m2(ii) in terms of/g. The molecular sieve is activated for 0.5h under the conditions of nitrogen carrier gas flow rate of 100ml/min and temperature of 500 ℃ and then subjected to MTO reaction evaluation, wherein the mass concentration of methanol is 95%, and the space velocity of methanol is 0.5h-1The mass selectivity of ethylene and propylene in the cracking gas respectively reaches 34.56 percent and 45.68 percent under the conditions that the reaction pressure is 0.2MPa and the reaction temperature is 420 ℃.
Example 8
69.5g of trimethyl adamantammonium (25 wt%), 1.8g of tetraethylammonium chloride and 12.8g of sodium hydroxide are weighed, 244.1g of deionized water is added, and the mixture is stirred and mixed uniformly; adding 1.6g of aluminum hydroxide into the solution, and stirring vigorously for 10 minutes; after the aluminum source is completely dissolved, 63.2g of coarse silica gel is slowly added, after 10 minutes of vigorous stirring, 1.9g of seed crystal (SZ-3) is added, and then vigorous stirring is continued for 2 hours to form gel. Transferring the obtained gel to a stainless steel crystallization kettle with a polytetrafluoroethylene lining, and dynamically crystallizing for 6 days at 160 ℃ at the motor rotating speed of 30 rpm/min. And after crystallization is finished, taking out the crystallization kettle, quenching the crystallization kettle by water to room temperature, centrifugally separating the product, washing the product to be neutral, drying the product in a dryer at 100 ℃ for 5 hours, and roasting the product at 600 ℃ for 4 hours at the heating rate of 1 ℃/min to obtain the sodium type molecular sieve.
Placing the roasted sodium type molecular sieve sample in NH with the concentration of 1.5mol/L4Ion exchange is carried out for 4 times in Cl solution, the exchange temperature is 70 ℃, the time of single ion exchange is 0.5h, and the ion exchange capacity is 0.1g (sodium type molecular sieve)/ml (NH)4Cl solution). And (3) drying the product after ion exchange at 100 ℃ for 5 hours after centrifugal separation, and roasting at 550 ℃ for 4 hours at the heating rate of 1 ℃/min to obtain the hydrogen type molecular sieve. The grain size of the obtained product is about 200nm, and the specific surface area is 658m2(ii) in terms of/g. The molecular sieve is activated for 2 hours under the conditions of nitrogen carrier gas flow rate of 60ml/min and temperature of 450 ℃ and then subjected to MTO reaction evaluation, wherein the mass concentration of methanol is 60 percent, and the space velocity of the methanol is 2 hours-1The mass selectivity of ethylene and propylene in the cracking gas respectively reaches 35.06% and 46.23% under the conditions that the reaction pressure is 0.2MPa and the reaction temperature is 350 ℃.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (11)
1. A process for the preparation of an olefin catalyst which is a hydrogen H-SSZ-13 molecular sieve for the preparation of olefins from methanol, comprising:
step (1): mixing a template agent, an auxiliary agent, sodium hydroxide and water, and uniformly stirring to obtain a mixed solution; adding an aluminum source into the mixed solution, and stirring until the aluminum source is dissolved; adding a silicon source into the mixed solution, and keeping vigorous stirring to obtain gel; wherein the silicon source, the aluminum source, the sodium hydroxide, the template agent, the auxiliary agent and the waterThe molar ratio of (A) to (B) is 100: 0.5-2: 10-20: 4-15: 0.1-2: 800-2400; the silicon source is SiO2The aluminum source is calculated by Al2O3The sodium hydroxide is calculated by Na2Measuring O;
step (2): placing the gel obtained in the step (1) in a hydrothermal reaction kettle, carrying out dynamic crystallization treatment, and carrying out centrifugal separation, washing, drying and roasting on the obtained product to obtain a sodium Na-SSZ-13 molecular sieve;
and (3): and (3) performing ammonia ion exchange, drying and roasting on the sodium type Na-SSZ-13 molecular sieve obtained in the step (2) to obtain the hydrogen type H-SSZ-13 molecular sieve.
2. The method for preparing an olefin catalyst according to claim 1, wherein the template agent is N, N, N-trimethyladamantammonium, and the auxiliary agent is tetraethylammonium chloride, tetraethylammonium bromide, or tetraethylammonium iodide.
3. The method for preparing an olefin catalyst according to claim 1 or 2, wherein the aluminum source is any one or a mixture of any two of aluminum hydroxide, aluminum sulfate, aluminum isopropoxide, pseudoboehmite, and sodium metaaluminate, preferably aluminum hydroxide; the silicon source is any one or a mixture of any two of nano silicon dioxide, silica sol, white carbon black and coarse pore silica gel, and the coarse pore silica gel is preferred.
4. The preparation method of the olefin catalyst according to any one of claims 1 to 3, wherein in the step (1), a silicon source is added and then a seed crystal is added, wherein the seed crystal is calcined Na-SSZ-13 or H-SSZ-13 in a sodium form or a hydrogen form, and the addition amount of the seed crystal is 0-5% of the mass of the silicon source and is not 0.
5. The method for preparing the olefin catalyst according to any one of claims 1 to 4, wherein the dynamic crystallization treatment is performed under the conditions of a motor rotation speed of 20 to 60rpm/min, a crystallization temperature of 150 to 180 ℃, and a crystallization time of 4 to 8 days.
6. The method for producing an olefin catalyst according to any one of claims 1 to 4, wherein the calcination conditions in the step (2) are: the roasting temperature is 550-600 ℃, the roasting time is 4-10 hours, and the heating rate is 0.5-2 ℃/min; preferably at a temperature of 600 c, preferably for a time of 4 hours, preferably at a temperature rise rate of 1 c/min.
7. The method for producing an olefin catalyst according to any one of claims 1 to 4, wherein the conditions for the ammonia ion exchange in step (3) are: 1 to 2mol/L NH40.01 to 0.2g of Na-SSZ-13/ml NH in an aqueous Cl solution4The Cl aqueous solution is subjected to ion exchange at the temperature of 60-80 ℃, the time of single ion exchange is 0.5-3 h, and the ion exchange times are 2-4; preferably 1mol/L NH4Aqueous Cl solution, 0.05g Na-SSZ-13/ml NH4Cl aqueous solution, ion exchange temperature of 70 ℃, single ion exchange time of 2h and ion exchange times of 3.
8. The method for producing an olefin catalyst according to any one of claims 1 to 4, wherein the calcination conditions in the step (3) are: the roasting temperature is 500-550 ℃, the roasting time is 4-6 hours, the heating rate is 0.5-2 ℃/min, the temperature is 550 ℃ preferably, the time is 4 hours preferably, and the heating rate is 1 ℃/min preferably.
9. An olefin catalyst, characterized in that it is prepared by the process for the preparation of an olefin catalyst according to any one of claims 1 to 8, having a particle size of less than 1 μm, preferably less than 200nm, and having a catalyst crystal morphology of cubic or cubic stacks.
10. A process for the preparation of olefins from methanol, characterized in that the process comprises the following steps: tabletting and sieving the olefin catalyst of claim 9, taking out the sieved coarse particle catalyst, loading the coarse particle catalyst into a fixed bed reactor, introducing nitrogen carrier gas with the flow rate of 30-100 mL/min, activating at 450-550 ℃ for 0.5-2 h, cooling to the reaction condition of preparing olefin from methanol, keeping the flow rate of the nitrogen carrier gas, and introducing methanol to obtain ethylene and propylene.
11. The method of claim 10, wherein the reaction conditions are as follows: the reaction temperature is 330-420 ℃, the reaction pressure is 0.1-0.8 MPa of absolute pressure, and the mass space velocity of the methanol is 0.5-5.0 h-1The mass concentration of the methanol is 50-95%.
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